WO2004046072A1 - Procede de production de 1,6-hexandiol d'un niveau de purete de plus de 99,5% - Google Patents

Procede de production de 1,6-hexandiol d'un niveau de purete de plus de 99,5% Download PDF

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Publication number
WO2004046072A1
WO2004046072A1 PCT/EP2003/012561 EP0312561W WO2004046072A1 WO 2004046072 A1 WO2004046072 A1 WO 2004046072A1 EP 0312561 W EP0312561 W EP 0312561W WO 2004046072 A1 WO2004046072 A1 WO 2004046072A1
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WO
WIPO (PCT)
Prior art keywords
ester
acid
cyclohexanediols
hydrogenation
mixture
Prior art date
Application number
PCT/EP2003/012561
Other languages
German (de)
English (en)
Inventor
Andrea Haunert
Rolf-Hartmuth Fischer
Thomas Krug
Tilman Sirch
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2003283386A priority Critical patent/AU2003283386A1/en
Publication of WO2004046072A1 publication Critical patent/WO2004046072A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • dicarboxylic acid solution is first esterified with a d-Cio-alkanol and the esterification mixture obtained is separated by distillation after removal of excess alcohol and other low boilers.
  • An ester fraction is obtained which is essentially free of 1,4-cyclohexanediols and a bottoms fraction containing 1,4-cyclohexanediols which essentially contains oligomeric and polymeric carboxylic acid esters.
  • 1, 6-hexanediol is produced from the ester fraction by hydrogenation with a purity of at least 99%.
  • Educts for the processes described in DE-A 196 07 954 and DE-A 196 07 955 for the preparation of 1,6-hexanediol are the aqueous solutions of carboxylic acids which are used in the oxidation of cyclohexane to cyclohexanol and cyclohexanone (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., 1987. Vol. A8, p. 49) are formed as by-products, hereinafter called dicarboxylic acid solution (DCL).
  • DCL dicarboxylic acid solution
  • ester fraction c) which, by separating the bottom product from the extraction of ester fraction b) in a second distillation stage into one of 1,4-cyclohexanediols essentially free ester fraction (ester fraction c)) and at least the greater part of the Fraction containing 1,4-cyclohexanediols is obtained.
  • An ester fraction essentially free of 1,4-cyclohexanediols means one with a content of less than 0.05% by weight of 1,4-cyclohexanediols.
  • the acetalization can be carried out with and without the addition of acidic catalysts, but preferably with the action of acidic catalysts.
  • This can be a homogeneous dissolved or a solid catalyst.
  • homogeneous catalysts are sulfuric acid, phosphoric acid, hydrochloric acid, sulfonic acids such as p-toluenesulfonic acid, heteropolyacids such as tungstophosphoric acid or Lewis acids such as e.g. Aluminum, vanadium, titanium, boron compounds called. Mineral acids, in particular sulfuric acid, are preferred.
  • the weight ratio of homogeneous catalyst to the mixture to be acetalized is generally 0.0001 to 0.5, preferably 0.001 to 0.3.
  • the acetalization can be carried out at 20 ° C. to 200 ° C., preferably at 40 to 100 ° C., particularly preferably at 40 to 80 ° C.
  • the residence time on the catalyst is preferably 0.5 to 600 min, particularly preferably 10 to 120 min.
  • the acetalization can be carried out in any process step of the processes described in DE-A 196 07 954 and DE-A 196 07 955 after the esterification. the, particularly preferably directly before the hydrogenation. In this particularly preferred case, the ester mixture c) is used as the starting material for the hydrogenation.
  • the process according to the invention can be carried out continuously, semi-continuously or batchwise.
  • Any water or excess acetalizing reagent (such as alcohol) formed during the reaction can be continuously e.g. through a membrane, or be removed by distillation.
  • ester mixture thus treated is optionally distilled, as in
  • Suitable catalysts are all homogeneous and heterogeneous catalysts suitable for the hydrogenation of carbonyl groups, such as metals, metal oxides, metal compounds or mixtures thereof.
  • the hydrogenation catalysts, in particular heterogeneous catalysts, described in more detail in DE-A 196 07 954 are preferably used.
  • the hydrogenation is carried out in a manner known per se as described in DE-A 196 07 954, in particular at 150 to 300 ° C. and at a pressure of 1 to 50 bar (in the case of hydrogenations in the gas phase over a fixed catalyst) or at a Pressure in the range of 30 to 350 bar (for hydrogenations in the liquid phase with a fixed or suspended catalyst).
  • the hydrogenation can be carried out batchwise, preferably continuously.
  • the hydrogenation consists essentially of 1, 6-hexanediol and the esterification alcohol.
  • Other components are 1, 5-pentanediol, 1, 4-butanediol, 1, 2-cyclohexanediols and small amounts of monoalcohols with 1 to 6 carbon atoms and water.
  • 1,4-cyclohexanediols which cannot be separated and which is 1,6-hexanediol is significantly reduced after the hydrogenation.
  • the hydrogenation discharge e.g. 1, 4-dimethoxycyclohexane, 4-methoxycyclohexan-1-ol, 1, 1 ⁇ 4,4-tetramethoxycyclohexane and 4,4-dimethoxycyclohexan-1-ol.
  • the hydrogenation output is fed into, for example, a membrane system or preferably a distillation column and into the esterification alcohol, which additionally contains the majority of the other low-boiling components and one Stream which contains predominantly 1,6-hexanediol in addition to 1,5-pentanediol but significantly less 1,4-cyclohexanediols is separated.
  • a pressure of 10 to 1500 mbar, preferably 30 to 1200 mbar, particularly preferably 50 to 1000 mbar head temperatures of 0 to 120 ° C., preferably 20 to 100 ° C., particularly preferably 30 to 90 ° C. and bottom temperatures from 100 to 270 ° C, preferably 140 to 260 ° C, particularly preferably 160 to 250 ° C.
  • the stream containing 1, 6-hexanediol is purified in a column.
  • 1, 5-Pentanediol, the 1, 2-cyclohexanediols and any other low boilers which may be present are removed overhead. If the 1,2-cyclohexanediols and / or 1,5-pentanediol are to be obtained as additional valuable products, they can be separated in a further column. Any existing high boilers are removed via the swamp.
  • 1,6-hexanediol with a significantly reduced 1,4-cyclohexanediol content of 0.005 to 0.1% by weight with a purity> 99.5% is taken from a side stream of the column.
  • the stages can also be combined in a batchwise fractional distillation.
  • the process according to the invention thus represents a simple and inexpensive procedure for obtaining highly pure 1,6-hexanediol with minimal amounts of 1,4-cyclohexanediols.
  • Example 1 a discontinuously
  • 0.1 kg ester mixture prepared according to DE-A 196 07 954 (approx. 55% dimethyl adipate and 20% methyl hydroxycaproate), which contains approx. 1300 ppm 1,4-cyclohexanedione, were mixed with 0.2 g acidic ion exchanger (Amberlyst ® 15 , From Fluka) and 5% by weight of MeOH. The mixture was stirred at 65 ° C. for 30 min and then filtered off from the acidic ion exchanger.
  • Example 1 c discontinuously
  • Example 1 d discontinuous
  • Example 1 e discontinuous
  • Example 1 f discontinuous
  • Example 1 g discontinuous
  • Example 1 h discontinuous
  • dicarboxylic acid solution (adipic acid approx. 17% by weight, approx. 13% 6-hydroxycaproic acid, approx. 1.5% by weight 1, 4-cyclohexanediols, approx. 0.08% by weight 1, 4 cyclohexane - Dione, approx. 45% water) were continuously in a distillation apparatus (three-bed bubble tray column with external oil heating circuit, oil temperature 150 ° C, tray volume approx. 25 ml each, feed via the bubble tray) with a packed column (approx. 4 theoretical Separation stages, no return at the head) distilled.
  • the top product obtained was 0.045 kg with a formic acid content in the water of about 3%.
  • the water content in the bottom stream (5.5 kg) was approximately 0.4%.
  • Level 2 (esterification)
  • the esterification stream from stage 2 was distilled in a column (1015 mbar, 65 ° C. top temperature, up to 125 ° C. bottom temperature). 7.0 kg were withdrawn overhead. 6.8 kg were obtained as the bottom product.
  • the bottom stream from stage 3 was fractionally distilled in a 50 cm packed column (1 mbar, head temperature 70 to 90 ° C., bottom temperature 180 ° C.).
  • the 1,4-cyclohexanediols were found in the sump.
  • stage 8 The discharge from stage 8 was fractionally distilled analogously to the apparatus described in stage 3. At 65 ° C top temperature 3.5 kg were distilled off (mainly methanol). 2.2 kg remained in the swamp.
  • stage 9 The bottom from stage 9 was fractionally distilled analogously to stage 4 up to a bottom temperature of 160 ° C.
  • the distillate obtained was 1.3 kg, which could be hydrogenated directly or recycled to the 4th stage.
  • Composition 52% methyl 6-hydroxycaproate, 31% dimethyl adipate, 5% dimethyl glutarate, 4% methyl 5-hydroxycaproate and a large number of other components which are insignificant in terms of quantity).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé permettant de produire du 1,6-hexandiol par hydrogénation d'alkylester d'acide adipique et d'alkylester d'acide 6-hydroxycapronique et de 1,4-cyclohexandione et de 4-hydroxycyclohexane-1-one, comme mélanges d'esters contenant des impuretés. Ledit procédé se caractérise en ce qu'avant hydrogénation, les mélanges d'esters sont traités avec un agent d'acétalisation. L'invention concerne également un procédé permettant de produire du 1,6-hexandiol par hydrogénation d'alkylester d'acide adipique et d'alkylester d'acide 6-hydroxycapronique et de 1,4-cyclohexandione et de 4-hydroxycyclohexane-1-one, comme mélange d'esters contenant des impuretés. Ledit procédé se caractérise en ce que pendant l'estérification d'un mélange d'acide dicarboxylique qui contient de l'acide adipique, de l'acide 6-hydroxycapronique et de faibles quantités de 1,4-cyclohexandiols et qui est obtenu sous forme de sous-produit lors de l'oxydation de cyclohexane en cyclohexanone/cyclohexanol avec de l'oxygène ou avec des gaz contenant de l'oxygène et par extraction d'eau du mélange de réaction, avec un alcool de faible poids moléculaire, un agent d'acétalisation différent dudit alcool de faible poids moléculaire est ajouté.
PCT/EP2003/012561 2002-11-19 2003-11-11 Procede de production de 1,6-hexandiol d'un niveau de purete de plus de 99,5% WO2004046072A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003283386A AU2003283386A1 (en) 2002-11-19 2003-11-11 Method for producing 1,6-hexanediol with a purity of greater than 99.5 %

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10253751.8 2002-11-19
DE10253751A DE10253751A1 (de) 2002-11-19 2002-11-19 Verfahren zur Herstellung von 1,6-Hexandiol in einer Reinheit von über 99,5%

Publications (1)

Publication Number Publication Date
WO2004046072A1 true WO2004046072A1 (fr) 2004-06-03

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AU (1) AU2003283386A1 (fr)
DE (1) DE10253751A1 (fr)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006005504A1 (fr) * 2004-07-09 2006-01-19 Basf Aktiengesellschaft Procede de production de 1,6-hexanediol d'une purete superieure a 99,5 %
WO2010063659A2 (fr) 2008-12-05 2010-06-10 Basf Se Procédé de préparation de 1,6-hexanediol
CN103616464A (zh) * 2013-08-28 2014-03-05 南通天泽化工有限公司 一种原乙酸三甲酯定量分析方法
CN113683483A (zh) * 2021-06-07 2021-11-23 浙江博聚新材料有限公司 一种高纯1,6-己二醇的生产方法及装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102351648B (zh) * 2011-09-09 2013-11-20 上海戊正工程技术有限公司 一种生产1,6-己二醇并联产ε-己内酯的工艺

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996020909A1 (fr) * 1995-01-05 1996-07-11 Basf Aktiengesellschaft Procede d'amelioration de la purete d'hexanediol-1,6
DE19607955A1 (de) * 1996-03-01 1997-09-04 Basf Ag Verfahren zur Herstellung von 1,6-Hexandiol mit einer Reinheit über 99 %

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996020909A1 (fr) * 1995-01-05 1996-07-11 Basf Aktiengesellschaft Procede d'amelioration de la purete d'hexanediol-1,6
DE19607955A1 (de) * 1996-03-01 1997-09-04 Basf Ag Verfahren zur Herstellung von 1,6-Hexandiol mit einer Reinheit über 99 %

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006005504A1 (fr) * 2004-07-09 2006-01-19 Basf Aktiengesellschaft Procede de production de 1,6-hexanediol d'une purete superieure a 99,5 %
US7449609B2 (en) 2004-07-09 2008-11-11 Basf Se Method for production of 1,6-hexanediol with a purity in excess of 99.5%
WO2010063659A2 (fr) 2008-12-05 2010-06-10 Basf Se Procédé de préparation de 1,6-hexanediol
WO2010063659A3 (fr) * 2008-12-05 2010-10-21 Basf Se Procédé de préparation de 1,6-hexanediol
CN103616464A (zh) * 2013-08-28 2014-03-05 南通天泽化工有限公司 一种原乙酸三甲酯定量分析方法
CN113683483A (zh) * 2021-06-07 2021-11-23 浙江博聚新材料有限公司 一种高纯1,6-己二醇的生产方法及装置
US11492316B1 (en) 2021-06-07 2022-11-08 Zhejiang Boju New Materials Co., Ltd. Production method and production device of high-purity 1,6-hexanediol

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Publication number Publication date
DE10253751A1 (de) 2004-06-03
AU2003283386A1 (en) 2004-06-15

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